CN115244016A

CN115244016A - Glass composition for glass fiber, glass fiber fabric, and glass fiber-reinforced resin composition

Info

Publication number: CN115244016A
Application number: CN202080098296.9A
Authority: CN
Inventors: 漆崎优; 细川贵庸; 野中贵史
Original assignee: Nitto Boseki Co Ltd
Current assignee: Nitto Boseki Co Ltd
Priority date: 2020-04-10
Filing date: 2020-12-24
Publication date: 2022-10-25
Also published as: EP4043415A4; KR20220167267A; EP4043415A1; TW202138328A; JPWO2021205699A1; US20220402810A1; WO2021205699A1

Abstract

The present invention provides a glass composition for glass fibers. The glass composition has a low dielectric loss tangent, suppresses the occurrence of phase separation, reduces the viscosity at high temperatures, and reduces the occurrence of striae. The glass composition for glass fiber contains 52.0 to 57.5 mass% of SiO ₂ 19.5 to 25.5 mass% of B ₂ O ₃ 8.0 to 13.0 mass% of Al ₂ O ₃ 0 to 2.0 mass% of MgO, 0 to 6.0 mass% of CaO, 0.5 to 6.5 mass% of SrO and 0.1 to 3.0 mass% of TiO ₂ ，Al ₂ O ₃ Relative to B ₂ O ₃ The content ratio of (A) is 0.35-0.54 ₂ Content ratios of (SI) and (B) ₂ O ₃ The content of B, mgOContent ratio of M, caO, content ratio of C, srO, content ratio SR and TiO ₂ The content ratio T satisfies the following formula (1): 6.90 ≤ 100 × (B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤12.30…(1)。

Description

Glass composition for glass fiber, glass fiber fabric, and glass fiber-reinforced resin composition

Technical Field

The present invention relates to a glass composition for glass fibers, glass fibers composed of the glass composition for glass fibers, a glass fiber fabric containing the glass fibers, and a glass fiber-reinforced resin composition containing the glass fibers.

Background

The glass fiber is manufactured in the following manner. A glass raw material prepared so as to be a glass composition for glass fibers having a desired composition is melted in a glass melting furnace to produce molten glass (a melt of the glass composition for glass fibers), the molten glass is discharged from a vessel (Bushing/blowing) having a nozzle plate in which several to several thousand nozzle tips are formed, and the molten glass is then cooled while being drawn by a high-speed winding method to be solidified into a fiber shape (hereinafter, this operation may be referred to as "spinning"). The sleeve is formed of a noble metal such as platinum.

Conventionally, glass fibers have been widely used in various applications because strength of resin molded articles can be improved, and the resin molded articles are increasingly used in housings or fittings of electronic devices such as servers, smart phones, and notebook computers.

In general, since glass absorbs energy as heat from an alternating current, when the resin molded article is used for a housing or a component of the electronic device, the resin molded article generates heat.

Here, the dielectric loss energy absorbed by the glass is proportional to the dielectric constant and the dielectric loss tangent determined by the composition and structure of the glass, and is represented by the following formula (a).

W＝kfv ² ×ε ^1/2 ×tanδ…(A)

Here, W represents dielectric loss energy, k represents a constant, f represents frequency, v ² Denotes a potential gradient, ε denotes a dielectric constant, and tan δ denotes a dielectric loss tangent. From the formula (A), it is understood that the higher the dielectric constant and the dielectric loss tangent, the higher the frequency, and the higher the dielectric loss, and the greater the heat generation of the resin molded article.

In recent years, due to the effect of the frequency (f in the formula (a)) of the alternating current used in the case or the component of the electronic device becoming high, a lower dielectric constant and a lower dielectric loss tangent are required for the glass fiber used in the case or the component of the electronic device in order to reduce the energy consumption for low dielectric loss. In particular, the dielectric loss tangent has a larger influence on the formula (a) than the dielectric constant of the square root, and therefore, it is required to realize a low dielectric loss tangent.

In order to provide a glass composition for glass fibers with a low dielectric constant and a low dielectric loss tangent and to achieve efficient glass fiberization in accordance with the above requirements, the present applicant has proposed the following glass composition for glass fibers (see patent document 1): as the glass composition for glass fiber which suppresses the generation of phase separation and, moreover, reduces the viscosity at high temperatures, it contains, relative to the total amount of the glass composition for glass fiber: siO in the range of 52.0 to 59.5 mass% ₂ And B in the range of 17.5 to 25.5 mass% ₂ O ₃ And 9.0 to 14.0 mass% of Al ₂ O ₃ 0.5 to 6.0 mass% of SrO, 1.0 to 5.0 mass% of MgO, 1.0 to 5.0 mass% of CaO, and 0.1 to 3.0 mass% of F in total ₂ And Cl ₂ . The phase separation refers to a phase separation phenomenon in which a single-phase glass forms glass phases having different compositions due to heat or the like. When phase separation occurs, the chemical durability of the glass fiber is reduced, and when phase separation occurs particularly remarkably, fiberization of the molten glass becomes difficult.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 6468409

Disclosure of Invention

Problems to be solved by the invention

However, when glass fibers formed from a glass composition for glass fibers in patent document 1 are mass-produced in an industrial manner using a glass melting furnace having a sleeve provided with a nozzle plate having 100 or more nozzle heads, there is a problem that the glass fibers are broken during spinning and the production efficiency is lowered.

The present inventors have made extensive studies on the reason for the above-described problems, and found that breakage of glass fibers during spinning is caused by the generation of striae. Here, in a glass melting furnace having a small shroud having a nozzle plate in which less than 100 nozzle heads are formed, the volume of the glass melting furnace is formed small in accordance with the size of the shroud, and therefore, the temperature in the glass melting furnace and the volatilization amount of the glass material are uniform. On the other hand, in the case of using a glass-melting furnace having a large-sized jacket tube which is required to form a nozzle plate having 100 or more nozzle heads, since the volume of the glass-melting furnace is formed to be large in accordance with the size of the jacket tube, there are cases where the temperature in the glass-melting furnace and the volatilization amount of the glass material vary, and the glass composition also varies due to the variation. Different kinds of glass generated by the deviation appear in a streak shape during melting, and a cord appears due to a difference in refractive index in the glass. When the beads are generated, when the molten glass is discharged from the bushing and drawn by winding at a high speed, a difference in composition occurs at a portion where the beads are generated, and thus a difference in viscosity occurs, and the viscosity difference hinders drawing of the molten glass, so that breakage of the glass fiber is likely to occur during spinning.

In order to solve the above-described problems, an object of the present invention is to provide a glass composition for glass fibers, which has a low dielectric loss tangent, suppresses the occurrence of phase separation, reduces the viscosity at high temperatures, and further reduces the occurrence of striae. Further, another object of the present invention is to provide a glass fiber formed from the glass composition for glass fiber, a glass fiber fabric comprising the glass fiber, and a glass fiber-reinforced resin composition using the glass fiber.

Means for solving the problems

In order to achieve the object, the glass composition for glass fibers of the present invention is characterized by containing, relative to the total amount of the glass composition for glass fibers: siO in the range of 52.0 to 57.5 mass% ₂ 19.5 to 25.5% by mass of B ₂ O ₃ And 8.0 to 13.0 mass% of Al ₂ O ₃ MgO in a range of 0 to 2.0 mass%, caO in a range of 0 to 6.0 mass%, srO in a range of 0.5 to 6.5 mass%, and TiO in a range of 0.1 to 3.0 mass% ₂ Said Al ₂ O ₃ Content of (B) based on the amount of B ₂ O ₃ Has a content (mass%) of 0.35 to 0.54, and the SiO ₂ Content ratio (mass%) of (B) SI ₂ O ₃ A content ratio (mass%) B of the above-mentioned MgO, a content ratio (mass%) M of the above-mentioned CaO, a content ratio (mass%) C of the above-mentioned SrO, a content ratio (mass%) SR of the above-mentioned SrO, and the above-mentioned TiO ₂ The content (mass%) T of (b) satisfies the following formula (1).

6.90≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2

≤12.30…(1)

The glass composition for glass fiber according to the present invention contains SiO in the above range ₂ 、B ₂ O ₃ 、Al ₂ O ₃ MgO, caO, srO and TiO ₂ ，Al ₂ O ₃ Relative to the content of B ₂ O ₃ When the content ratio of (b) is in the above range and the formula (1) is satisfied, the low dielectric loss tangent is obtained, the occurrence of phase separation is suppressed, and the viscosity at high temperature is reducedAnd moreover, the generation of the wave rib is further reduced.

The term "having a low dielectric loss tangent" as used herein means that the dielectric loss tangent is 0.0018 or less at a frequency of 10 GHz. The viscosity decrease at high temperature means that the 1000 poise temperature (temperature at which the viscosity of the molten glass is 1000 poise (100 pas)) is 1375 ℃ or lower.

In addition, the glass composition for glass fiber of the present invention preferably satisfies the following formula (2) in terms of SI, B, M, C, SR and T.

9.56≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.77…(2)

When the SI, B, M, C, SR, and T satisfy the formula (2), the glass composition for glass fibers of the present invention can more reliably have a low dielectric loss tangent, more reliably suppress the occurrence of phase separation, more reliably reduce the viscosity at high temperatures, and more reliably reduce the occurrence of striae.

Further, the glass composition for glass fiber of the present invention preferably satisfies the following formula (3) in terms of SI, B, M, C, SR and T.

10.00≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.35…(3)

When the SI, B, M, C, SR, and T satisfy the formula (3), the glass composition for glass fibers of the present invention has a lower dielectric loss tangent, and can more reliably suppress the occurrence of phase separation, more reliably reduce the viscosity at high temperatures, and further reduce the occurrence of striae.

Here, the dielectric loss tangent having a lower value means that the dielectric loss tangent is 0.0017 or less at a frequency of 10 GHz.

In addition, the glass composition for glass fiber of the present invention is particularly preferred that the SI, B, M, C, SR and T satisfy the following formula (4).

10.15≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.85…(4)

When the SI, B, M, C, SR, and T satisfy the formula (4), the glass composition for glass fiber of the present invention can more reliably have a lower dielectric loss tangent, more reliably suppress the occurrence of phase separation, further reduce the viscosity at high temperatures, and further more reliably reduce the occurrence of striae.

It should be noted that the viscosity at a high temperature is further decreased here means that the 1000 poise temperature (temperature at which the viscosity of the molten glass is 1000 poise (100 pas)) is less than 1370 ℃.

Further, in the glass composition for glass fiber of the present invention, it is most preferable that SI, B, M, C, SR and T satisfy the following formula (5).

10.35≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.78…(5)

By satisfying the above-mentioned SI, B, M, C, SR, and T with the above-mentioned formula (5), the glass composition for glass fibers of the present embodiment can more reliably provide a lower dielectric loss tangent, more reliably suppress the occurrence of phase separation, more reliably reduce the viscosity at high temperatures, and more reliably reduce the occurrence of cord.

The glass fiber of the present invention is composed of the glass composition for glass fiber of the present invention described above. The glass fiber of the present invention can be obtained, for example, by: the glass composition for glass fiber of the present invention is melted, and the obtained melt is ejected from a bushing having a nozzle plate with 1 to 8000 nozzle heads or holes formed thereon, and is wound at high speed, and is cooled while being drawn, and solidified to form a fiber shape. Accordingly, the glass fiber of the present invention has the same glass composition as the glass composition for glass fiber of the present invention described above.

The glass fiber fabric of the present invention comprises the glass fiber of the present invention.

The glass fiber-reinforced resin composition of the present invention contains the above-described glass fiber of the present invention. In the glass fiber-reinforced resin composition containing a resin (thermoplastic resin or thermosetting resin), glass fibers and other additives, the glass fiber-reinforced resin composition of the present invention contains, for example, 10 to 90 mass% of glass fibers with respect to the total amount of the glass fiber-reinforced resin composition.

Detailed Description

Next, embodiments of the present invention will be described in more detail.

The glass composition for glass fiber of the present embodiment contains, relative to the total amount of the glass composition for glass fiber: siO in the range of 52.0 to 57.5 mass% ₂ 19.5 to 25.5% by mass of B ₂ O ₃ 8.0 to 13.0 mass% of Al ₂ O ₃ MgO in a range of 0 to 2.0 mass%, caO in a range of 0 to 6.0 mass%, srO in a range of 0.5 to 6.5 mass%, and TiO in a range of 0.1 to 3.0 mass% ₂ ，Al ₂ O ₃ Content ratio (mass%) of (B) to the B ₂ O ₃ Has a content (mass%) of 0.35 to 0.54, and the SiO ₂ Content ratio (mass%) of (B) SI ₂ O ₃ A content (mass%) B of the above-mentioned MgO, a content (mass%) M of the above-mentioned CaO, a content (mass%) C of the above-mentioned SrO, a content (mass%) SR of the above-mentioned SrO, and the above-mentioned TiO ₂ The content ratio (mass%) T of (b) satisfies the above formula (1). Thus, according to the glass composition for glass fiber, siO is contained in the above range ₂ 、B ₂ O ₃ 、Al ₂ O ₃ MgO, caO, srO and TiO ₂ And Al ₂ O ₃ Relative to the content of B ₂ O ₃ When the content ratio of (b) is within the above range and the formula (1) is satisfied, the glass composition for glass fiber has a low dielectric loss tangent, suppresses occurrence of phase separation, reduces viscosity at high temperature, and further reduces occurrence of striae.

In the glass composition for glass fiber of the present embodiment, if SiO ₂ A content of less than 52.0 mass% based on the total amount of the glass composition used for the glass fiberThe mechanical strength of the glass fiber formed of the glass composition of the glass fiber is greatly reduced, and the function of the glass fiber as a reinforcing material in the glass fiber-reinforced resin composition is impaired. In addition, the glass fiber is susceptible to deterioration when exposed to an acidic environment. On the other hand, if SiO is used ₂ When the content of the total amount of the glass composition used for the glass fiber exceeds 57.5 mass%, the viscosity at high temperature increases, and the temperature of the molten glass material increases, and therefore, the glass fiber is not suitable for industrial production of glass fibers using a glass melting furnace equipped with a sleeve of a nozzle plate in which 100 or more nozzle heads are required to be formed, from the viewpoint of production cost.

In the glass composition for glass fiber of the present embodiment, siO ₂ The content ratio with respect to the total amount of the glass composition used for the glass fiber is preferably 52.5% by mass or more and 55.5% by mass or less, more preferably 53.1% by mass or more and 55.0% by mass or less, further preferably 53.3% by mass or more and 54.7% by mass or less, particularly preferably 53.5% by mass or more and 54.3% by mass or less, and most preferably 53.6% by mass or more and 54.2% by mass or less.

In the glass composition for glass fiber of the present embodiment, if B ₂ O ₃ When the content of the glass composition for glass fibers is less than 19.5% by mass based on the total amount of the glass composition for glass fibers, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently lowered. On the other hand, if B ₂ O ₃ When the content of the glass composition relative to the total amount of the glass composition used for the glass fiber exceeds 25.5 mass%, the occurrence of phase separation cannot be sufficiently suppressed regardless of the content of other components.

In the glass composition for glass fiber of the present embodiment, B ₂ O ₃ The content ratio with respect to the total amount of the glass composition used for the glass fibers is preferably 22.5% by mass or more and 24.8% by mass or less, more preferably 22.8% by mass or more and 24.7% by mass or less, still more preferably 23.0% by mass or more and 24.6% by mass or less, particularly preferably 23.1% by mass or more and 24.5% by mass or less, and most preferablyPreferably 23.2 mass% or more and 24.4 mass% or less.

In the glass composition for glass fiber of the present embodiment, if Al is contained ₂ O ₃ When the content of the glass composition relative to the total amount of the glass composition used for the glass fiber is less than 8.0 mass%, the occurrence of phase separation cannot be sufficiently suppressed regardless of the content of other components. On the other hand, if Al ₂ O ₃ When the content of the glass composition for glass fibers exceeds 13.0 mass%, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently reduced.

In the glass composition for glass fiber of the present embodiment, al ₂ O ₃ The content ratio with respect to the total amount of the glass composition used for the glass fibers is preferably 11.1% by mass or more and 12.9% by mass or less, more preferably 11.4% by mass or more and 12.8% by mass or less, still more preferably 11.6% by mass or more and 12.7% by mass or less, particularly preferably 11.9% by mass or more and 12.6% by mass or less, and most preferably 12.0% by mass or more and 12.5% by mass or less.

In the glass composition for glass fibers of the present embodiment, if the content of MgO with respect to the total amount of the glass composition for glass fibers exceeds 2.0 mass%, the generation of striae cannot be sufficiently reduced regardless of the content of other components.

In the glass composition for glass fibers of the present embodiment, the content of MgO with respect to the total amount of the glass composition for glass fibers is preferably 0% by mass or more and 1.4% by mass or less, more preferably 0% by mass or more and 1.1% by mass or less, further preferably 0% by mass or more and 0.9% by mass, particularly preferably 0% by mass or more and 0.7% by mass or less, and most preferably 0% by mass or more and 0.5% by mass or less.

In the glass composition for glass fibers of the present embodiment, if the content of CaO relative to the total amount of the glass composition for glass fibers exceeds 6.0 mass%, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently reduced while suppressing occurrence of phase separation.

In the glass composition for glass fibers of the present embodiment, the content of CaO relative to the total amount of the glass composition for glass fibers is preferably 1.5% by mass or more and 5.5% by mass or less, more preferably 2.0% by mass or more and 5.3% by mass or less, further preferably 2.5% by mass or more and 5.2% by mass or less, particularly preferably 2.8% by mass or more and 5.1% by mass or less, particularly preferably 3.0% by mass or more and 5.0% by mass or less, and most preferably 3.0% by mass or more and 4.9% by mass or less.

In the glass composition for glass fibers of the present embodiment, if the content of SrO is less than 0.5% by mass or exceeds 6.5% by mass relative to the total amount of the glass composition for glass fibers, the dielectric loss tangent of the glass composition for glass fibers cannot be sufficiently lowered.

In the glass composition for glass fibers of the present embodiment, the content of SrO with respect to the total amount of the glass composition for glass fibers is preferably 1.5% by mass or more and 6.0% by mass or less, more preferably 2.0% by mass or more and 5.5% by mass or less, further preferably 2.2% by mass or more and 5.3% by mass or less, particularly preferably 2.3% by mass or more and 5.2% by mass or less, particularly preferably 2.5% by mass or more and 4.7% by mass or less, and most preferably 2.8% by mass or more and 4.5% by mass or less.

In the glass composition for glass fiber of the present embodiment, if TiO is used ₂ When the content of the total amount of the glass composition used for the glass fiber is less than 0.1 mass%, the viscosity at high temperatures increases, and the temperature required for melting the glass material increases, and therefore, the glass composition is not suitable for industrial production of glass fibers using a glass melting furnace equipped with a sleeve of a nozzle plate on which 100 or more nozzle heads are to be formed, from the viewpoint of production cost. On the other hand, if TiO ₂ When the content of the glass composition for glass fiber exceeds 3.0 mass%, the dielectric loss tangent of the glass composition for glass fiber cannot be sufficiently lowered.

In the present embodiment, the glass fiberIn the glass composition of vitamin, tiO ₂ The content ratio with respect to the total amount of the glass composition used for the glass fibers is preferably 0.2% by mass or more and 2.8% by mass or less, more preferably 0.2% by mass or more and 2.7% by mass or less, still more preferably 0.3% by mass or more and 2.6% by mass or less, particularly preferably 0.4% by mass or more and 2.5% by mass or less, and most preferably 0.5% by mass or more and 2.0% by mass or less.

In the glass composition for glass fiber of the present embodiment, F ₂ And Cl ₂ The total content of the glass composition with respect to the total amount of the glass composition used for the glass fibers may be 0.1 mass% or more and 2.0 mass% or less. The glass composition for glass fiber of the present embodiment is formed by containing F in a total content ratio within the above range ₂ And Cl ₂ And helps to reduce the viscosity at high temperatures. On the other hand, if F ₂ And Cl ₂ If the total content exceeds 2.0 mass%, the chemical durability of the glass composition used for the glass fiber may be deteriorated.

The glass composition for glass fiber of the present embodiment contains F ₂ And Cl ₂ In the case of (A), F ₂ And Cl ₂ The total content ratio with respect to the total amount of the glass composition used for the glass fibers is preferably 0.2% by mass or more and 1.8% by mass or less, more preferably 0.5% by mass or more and 1.5% by mass or less, further preferably 0.6% by mass or more and 1.4% by mass or less, particularly preferably 0.7% by mass or more and 1.3% by mass or less, particularly preferably 0.8% by mass or more and 1.2% by mass or less, and most preferably 0.8% by mass or more and 1.0% by mass or less.

The glass composition for glass fiber according to the present embodiment contains F ₂ In the case of (A), F ₂ The content ratio with respect to the total amount of the glass composition used for the glass fiber is preferably 0.2% by mass or more and 1.8% by mass or less, more preferably 0.5% by mass or more and 1.5% by mass or less, still more preferably 0.6% by mass or more and 1.4% by mass or less, particularly preferably 0.7% by mass or more and 1.3% by mass or less, particularly preferably 0.8% by mass or more and 1.2% by mass or less, and most preferably 0.2% by mass or more and 1.2% by mass or less0.8 to 1.0 mass%.

The glass composition for glass fiber according to the present embodiment contains 0.4 mass% or more of F ₂ In the case (3), substantially no Cl may be contained ₂ (i.e., cl) ₂ The content of (b) may be less than 0.01 mass%).

The glass composition for glass fibers of the present embodiment may contain ZnO in a content ratio of 0 to 3.0 mass% with respect to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers of the present embodiment contains ZnO, if the content of ZnO exceeds 3.0 mass%, devitrification is likely to occur, and stable glass fiber production cannot be performed.

When the glass composition for glass fibers of the present embodiment contains ZnO, the content of ZnO based on the total amount of the glass composition for glass fibers is preferably 2.5% by mass or less, more preferably 1.5% by mass or less, and still more preferably 0.5% by mass or less.

The glass composition for glass fibers of the present embodiment may contain Fe in a content ratio of 0 mass% or more and 1.0 mass% or less with respect to the total amount of the glass composition for glass fibers ₂ O ₃ . The glass composition for glass fiber according to the present embodiment contains Fe ₂ O ₃ In the case of (2), from the viewpoint of suppressing bubbles contained in the glass fibers, it is effective to use Fe ₂ O ₃ The content of (b) is in a range of 0.1 to 0.6 mass%.

The glass composition for glass fibers of the present embodiment may contain SnO in a content ratio of 0 mass% or more and 1.0 mass% or less with respect to the total amount of the glass composition for glass fibers ₂ . The glass composition for glass fiber according to the present embodiment contains SnO ₂ In the case of (2), from the viewpoint of suppressing bubbles contained in the glass fibers, it is effective to use SnO ₂ The content of (b) is in a range of 0.1 to 0.6 mass%.

In the glass composition for glass fiber of the present embodiment, as long as Na is present ₂ O、K ₂ O and Li ₂ When the total content of O with respect to the total amount of the glass composition for glass fibers is less than 1.0 mass% and the content of each component is less than 0.4 mass%, na may be contained in the glass composition for glass fibers ₂ O、K ₂ O or Li ₂ And O. When Na is present ₂ O、K ₂ O and Li ₂ When the total content of O with respect to the total amount of the glass composition for glass fibers is 1.0 mass% or more, or the content of each component is 0.4 mass% or more, the dielectric constant and the dielectric loss tangent of the glass composition for glass fibers are greatly deteriorated.

In the glass composition for glass fiber of the present embodiment, as long as ZrO ₂ When the content of ZrO may be less than 0.4% by mass based on the total amount of the glass composition for glass fibers ₂ . When ZrO ₂ When the content of the glass composition is 0.4 mass% or more based on the total amount of the glass composition used for the glass fiber, devitrification is likely to occur, and stable production of the glass fiber cannot be performed.

In the glass composition for glass fiber of the present embodiment, if Cr is contained ₂ O ₃ Cr may be contained in an amount of less than 0.05% by mass based on the total amount of the glass composition for glass fibers ₂ O ₃ . When Cr is present ₂ O ₃ When the content of the glass composition is 0.05 mass% or more based on the total amount of the glass composition used for glass fibers, devitrification is likely to occur, and stable production of glass fibers cannot be performed.

The glass composition for glass fibers of the present embodiment may contain, as impurities derived from raw materials, oxides of Ba, P, mn, co, ni, cu, mo, W, ce, Y, and La in a total content ratio of less than 1.0 mass% with respect to the total amount of the glass composition for glass fibers. In particular, the glass composition for glass fiber of the present embodiment contains BaO and P ₂ O ₅ 、CeO ₂ 、Y ₂ O ₃ Or La ₂ O ₃ In the case of the presence of impurities,the content of each of the above impurities is preferably less than 0.40% by mass, more preferably less than 0.20% by mass, still more preferably less than 0.10% by mass, particularly preferably less than 0.05% by mass, and most preferably less than 0.01% by mass, respectively.

In addition, bi as an impurity derived from a raw material is contained in the glass composition for glass fiber of the present embodiment ₂ O ₃ 、Gd ₂ O ₃ 、Pr ₂ O ₃ 、Sc ₂ O ₃ Or Yb ₂ O ₃ In the case of (2), the content of each impurity is preferably less than 0.10% by mass, more preferably less than 0.05% by mass, and still more preferably less than 0.01% by mass, respectively.

In the glass composition for glass fiber of the present embodiment, siO ₂ 、B ₂ O ₃ 、Al ₂ O ₃ MgO, caO, srO and TiO ₂ The total content of (b) is 97.0% by mass or more, preferably 97.5% by mass or more, more preferably 98.0% by mass or more, further preferably 98.5% by mass or more, particularly preferably 98.8% by mass or more, and most preferably 99.0% by mass.

In the glass composition for glass fiber of the present embodiment, al ₂ O ₃ Content of (B) based on the amount of B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) Is in the range of 0.35 to 0.54. If B is present ₂ O ₃ Content of (2) and Al ₂ O ₃ Has a content ratio in the above range and Al ₂ O ₃ /B ₂ O ₃ If the amount is less than 0.35, the occurrence of phase separation cannot be sufficiently suppressed. On the other hand, if B ₂ O ₃ Content of (2) and Al ₂ O ₃ Has a content ratio in the above range and Al ₂ O ₃ /B ₂ O ₃ If the dielectric loss tangent exceeds 0.54, the dielectric loss tangent cannot be sufficiently reduced or the occurrence of cord cannot be sufficiently reduced.

In the glass composition for glass fiber of the present embodiment, al ₂ O ₃ Content of (B) based on the amount of B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) Preferably, the content is in the range of 0.49 to 0.53, more preferably in the range of 0.50 to 0.53, and still more preferably in the range of 0.50 to 0.52.

In the glass composition for glass fiber of the present embodiment, the SiO ₂ Content ratio (mass%) of (B) in (C) ₂ O ₃ A content (mass%) B of the above-mentioned MgO, a content (mass%) M of the above-mentioned CaO, a content (mass%) C of the above-mentioned SrO, a content (mass%) SR of the above-mentioned SrO, and the above-mentioned TiO ₂ The content (mass%) T of (B) satisfies the following formula (1).

6.90≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤12.30…(1)

When the SI, B, M, C, SR, and T satisfy the formula (1), the glass composition for glass fibers of the present embodiment has a low dielectric loss tangent, suppresses the occurrence of phase separation, reduces the viscosity at high temperatures, and reduces the occurrence of striae.

In the glass composition for glass fiber according to the present embodiment, SI, B, M, C, SR, and T preferably satisfy the following formula (2).

9.56≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.77…(2)

By making the SI, B, M, C, SR, and T satisfy the above formula (2), the glass composition for glass fibers of the present embodiment can more reliably have a low dielectric loss tangent, more reliably suppress the occurrence of phase separation, and more reliably reduce the viscosity at high temperatures, thereby more reliably reducing the occurrence of striae.

When the above SI, B, M, C, SR, and T satisfy the above formula (2), the glass composition for glass fibers of the present embodiment preferably contains, with respect to the total amount of the glass composition for glass fibers: 53.1 to 55.0 mass% of SiO ₂ And B in a range of 22.5 to 24.8 mass% ₂ O ₃ 11.1 to 12.9 mass% inclusiveRange of Al ₂ O ₃ MgO in a range of 0 to 1.4 mass%, caO in a range of 1.5 to 5.5 mass%, srO in a range of 1.5 to 6.0 mass%, and TiO in a range of 0.4 to 2.5 mass% ₂ ，Al ₂ O ₃ Content of (B) based on the above B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) In the range of 0.49 to 0.53.

In the glass composition for glass fiber of the present embodiment, SI, B, M, C, SR, and T preferably satisfy the following formula (3).

10.00≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.35…(3)

When the SI, B, M, C, SR, and T satisfy the formula (3), the glass composition for glass fiber according to the present embodiment has a lower dielectric loss tangent, can more reliably suppress the occurrence of phase separation, can more reliably reduce the viscosity at high temperatures, and can further reduce the occurrence of striae.

When the SI, B, M, C, SR, and T satisfy the formula (3), the glass composition for glass fiber of the present embodiment preferably contains, with respect to the total amount of the glass composition for glass fiber: 53.1 mass% or more and 5.0 mass% or less of SiO ₂ And B in a range of 22.5 to 24.8 mass% ₂ O ₃ 11.1 to 12.9 mass% of Al ₂ O ₃ MgO in a range of 0 to 1.4 mass%, caO in a range of 2.5 to 5.5 mass%, srO in a range of 2.5 to 4.7 mass%, and TiO in a range of 0.4 to 2.5 mass% ₂ ，Al ₂ O ₃ Content of (B) based on the above B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) In the range of 0.50 to 0.53.

In the glass composition for glass fiber of the present embodiment, it is particularly preferable that the SI, B, M, C, SR, and T satisfy the following formula (4).

10.15≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.85…(4)

When the SI, B, M, C, SR, and T satisfy the formula (4), the glass composition for glass fibers according to the present embodiment can more reliably have a lower dielectric loss tangent, can more reliably suppress the occurrence of phase separation, and can further reduce the viscosity at high temperatures, thereby more reliably reducing the occurrence of striae.

When the SI, B, M, C, SR, and T satisfy the formula (4), the glass composition for glass fibers of the present embodiment preferably contains, with respect to the total amount of the glass composition for glass fibers: 53.1 to 54.3 mass% of SiO ₂ And B in a range of 23.1 to 24.5 mass% ₂ O ₃ 11.6 to 12.7 mass% of Al ₂ O ₃ MgO in a range of 0 to 1.1 mass%, caO in a range of 2.5 to 5.5 mass%, srO in a range of 2.5 to 4.7 mass%, and TiO in a range of 0.4 to 2.5 mass% ₂ ，Al ₂ O ₃ Content ratio (mass%) of (B) to the B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) In the range of 0.50 to 0.53.

In the glass composition for glass fiber according to the present embodiment, SI, B, M, C, SR, and T most preferably satisfy the following formula (5).

10.35≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.78…(5)

By making the SI, B, M, C, SR, and T satisfy the formula (5), the glass composition for glass fibers according to the present embodiment can more reliably have a lower dielectric loss tangent, can more reliably suppress the occurrence of phase separation, can more reliably reduce the viscosity at high temperatures, and can more reliably reduce the occurrence of striae.

When the SI, B, M, C, SR, and T satisfy the formula (5), the glass composition for glass fiber of the present embodiment preferably contains, with respect to the total amount of the glass composition for glass fiber: 53.1 to 54.2 mass% of SiO ₂ 23.1 to 24.4 mass% of B ₂ O ₃ 11.6-12.5% by mass of Al ₂ O ₃ MgO in a range of 0 to 1.1 mass%, caO in a range of 2.5 to 5.0 mass%, srO in a range of 3.0 to 4.7 mass%, and TiO in a range of 0.5 to 2.5 mass% ₂ ，Al ₂ O ₃ Content of (B) based on the above B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) In the range of 0.50 to 0.52.

In the glass composition for glass fiber of the present embodiment, for the measurement of the content of each component, the content of Li as a light element may be measured using an ICP emission spectrometer, and the content of other elements may be measured using a wavelength dispersion fluorescent X-ray analyzer.

As a method for measuring the content, the following method can be employed: first, a glass batch (a material prepared by mixing glass raw materials) or a glass fiber (when an organic substance is adhered to the surface of a glass fiber or when a glass fiber is mainly contained as a reinforcing material in an organic substance (resin), for example, when the glass fiber is heated in a muffle furnace at 300 to 650 ℃ for about 0.5 to 24 hours, or the like, and the organic substance is removed and then used) is put in a platinum crucible, and is kept at a temperature of 1550 ℃ in the case of a glass batch or at a temperature of 1400 ℃ in the case of a glass fiber in an electric furnace for 6 hours, and is melted while being stirred, thereby obtaining a homogeneous molten glass. Next, the obtained molten glass was poured onto a carbon plate to prepare glass chips, which were then pulverized into powder to obtain glass powder. For the measurement of Li as a light element, the glass powder was thermally decomposed with an acid, and then quantitatively analyzed with an ICP emission spectrometer. For the measurement of other elements, after the glass powder was molded into a disk shape by a press, quantitative analysis was performed using a wavelength dispersive fluorescent X-ray analyzer. The quantitative analysis results were converted into oxides, the contents and total amounts of the respective components were calculated, and the contents of the respective components were determined from these values.

The glass composition for glass fiber according to the present embodiment can be obtained by melting glass raw materials (glass batch materials) that are blended so as to have the above-described composition after melting and solidifying, and then cooling and solidifying the molten glass raw materials.

In the glass composition for glass fiber of the present embodiment, the 1000 poise temperature is in the range of 1330 to 1400 ℃, preferably in the range of 1340 to 1390 ℃, more preferably in the range of 1345 to 1380 ℃, and still more preferably in the range of 1350 to 1375 ℃. In the glass composition for glass fiber of the present invention, the liquidus temperature (the temperature at which crystallization first occurs when the temperature of the molten glass is lowered) is in the range of 1050 to 1240 ℃, preferably 1100 to 1210 ℃, more preferably 1130 to 1200 ℃, and still more preferably 1150 to 1195 ℃. In the glass composition for glass fiber of the present invention, the temperature range (working temperature range) between the 1000 poise temperature and the liquidus temperature is 200 ℃ or more, preferably 200 to 400 ℃, and more preferably 210 to 360 ℃.

When the glass composition for glass fiber of the present embodiment is used to form glass fiber of the present embodiment, first, the glass raw material prepared as described above is supplied to a glass melting furnace, and the glass raw material is melted in the temperature range of 1000 poise or higher, specifically, in the range of 1450 to 1550 ℃. Then, the molten glass melted to the above temperature is ejected from 100 to 8000 nozzle heads or holes controlled to have a predetermined temperature, and is drawn and cooled at a high speed to solidify the glass, thereby forming glass fibers.

Here, the glass monofilament fiber (glass filament) which is ejected from 1 nozzle head or hole and cooled and solidified usually has a right circular cross-sectional shape and a diameter of 3.0 to 35.0. Mu.m. In applications where low dielectric characteristics are required, the diameter of the glass filaments is preferably in the range of 3.0 to 6.0. Mu.m, and more preferably in the range of 3.0 to 4.5. Mu.m. On the other hand, when the nozzle head has a non-circular shape and has a protrusion and/or a notch for rapidly cooling the molten glass, a glass filament having a non-circular (for example, elliptical or oval) cross-sectional shape can be obtained by controlling the temperature conditions. When the glass filaments have an elliptical or oval cross-sectional shape, the ratio of the major axis to the minor axis (major axis/minor axis) of the cross-sectional shape is, for example, in the range of 2.0 to 10.0, and the fiber diameter when the cross-sectional area is converted into a perfect circle (converted fiber diameter) is in the range of 3.0 to 35.0 μm.

The glass fiber of the present embodiment is generally in the form of a glass fiber bundle (glass strand) in which 10 to 8000 glass filaments are bundled, and has a weight in the range of 1 to 10000tex (g/km). The glass filaments discharged from the plurality of nozzle heads or orifices may be bundled into 1 glass fiber bundle, or may be bundled into a plurality of glass fiber bundles.

The glass fiber of the present embodiment may be in various forms such as yarn, woven fabric, knitted fabric, nonwoven fabric (including chopped strand mat and multiaxial nonwoven fabric), chopped strand, roving, and powder obtained by further processing the above glass strand.

The surfaces of the glass fibers of the present embodiment may be coated with an organic material for the purpose of improving the bundling property of the glass filaments, improving the adhesion between the glass fibers and the resin, improving the uniform dispersibility of the glass fibers in a mixture of the glass fibers and the resin or the inorganic material, and the like. Examples of such organic substances include: starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (particularly carboxylic acid-modified polypropylene), (poly) carboxylic acid (particularly maleic acid) and unsaturated monomer copolymer, and the like. The glass fiber of the present embodiment may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like, in addition to the resin. The glass fiber of the present embodiment may be coated with a treatment agent composition containing a silane coupling agent, a surfactant, and the like, without containing the resin. The resin composition or the treating agent composition covers the glass fiber in a ratio of 0.03 to 2.0 mass% based on the mass of the glass fiber of the present embodiment in a state of not being covered with the resin composition or the treating agent composition. The process of coating the glass fibers with the organic substance can be performed, for example, by the following method: in the process of producing glass fibers, a resin solution or a resin composition solution is applied to glass fibers by a known method such as a roll coater, and then the glass fibers to which the resin solution or the resin composition solution is applied are dried. In addition, the coating process may be performed by: the glass fiber of the present embodiment in the form of a woven fabric is immersed in a solution of the treating agent composition, and then the glass fiber to which the treating agent composition is applied is dried.

Here, examples of the silane coupling agent include: aminosilanes (gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-anilinopropyltrimethoxysilane, etc.), chlorosilanes (gamma-chloropropyltrimethoxysilane, etc.), epoxysilanes (beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, etc.), mercaptosilanes (gamma-mercaptotrimethoxysilane, etc.), vinylsilanes (vinyltrimethoxysilane, N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane, etc.), and (meth) acrylic silanes (gamma-methacryloxypropyltrimethoxysilane, etc.). In the present embodiment, the silane coupling agent may be used alone, or two or more of the silane coupling agents may be used in combination.

Examples of the lubricant include: modified silicone oil, animal oil (e.g., beef tallow) and the hydrogenated product thereof, vegetable oil (e.g., soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil) and the hydrogenated product thereof, animal wax (e.g., beeswax and wool), plant wax (e.g., candelilla wax and carnauba wax), mineral wax (e.g., paraffin wax and montan wax), a condensate of a higher saturated fatty acid and a higher saturated alcohol (e.g., a stearate such as lauryl stearate), polyethyleneimine, a polyalkylaminoalkyllinolenyl glycoside derivative, a fatty acid amide (e.g., a dehydration condensate of a polyethylene polyamine such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine and a fatty acid such as lauric acid, myristic acid, palmitic acid, and stearic acid), and a quaternary ammonium salt (e.g., an alkyltrimethylammonium salt such as lauryltrimethylammonium chloride). In the present embodiment, the above-mentioned lubricants may be used alone, or two or more of the above-mentioned lubricants may be used in combination.

Examples of the surfactant include: nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In the present embodiment, the surfactant may be used alone, or two or more of the surfactants may be used in combination.

Examples of the nonionic surfactant include: ethylene oxide propylene oxide alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid monoester, polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester ethylene oxide adduct, polyoxyethylene stearyl ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, glycerin fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol anhydride fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylenic glycol, acetylenic alcohol, ethylene oxide adduct of acetylenic glycol, ethylene oxide adduct of acetylenic alcohol.

Examples of the cationic surfactant include: alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkyl amine salt (acetate or hydrochloride, etc.), ethylene oxide adduct to higher alkyl amine, condensate of higher fatty acid and polyalkylene polyamine, ester salt of higher fatty acid and alkanolamine, salt of higher fatty acid amide, imidazoline type cationic surfactant, and alkyl pyridinium salt.

Examples of the anionic surfactant include: higher alcohol sulfuric acid ester salts, higher alkyl ether sulfuric acid ester salts, α -olefin sulfuric acid ester salts, alkylbenzenesulfonic acid salts, α -olefin sulfonic acid salts, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphoric acid ester salts, and higher alcohol ethylene oxide adducts.

Examples of the amphoteric surfactant include: amino acid type amphoteric surfactants such as alkali metal alkyl aminopropionates, betaine type amphoteric surfactants such as alkyldimethylbetaines, and imidazoline type amphoteric surfactants.

The glass fiber fabric of the present embodiment includes the glass fiber of the present embodiment described above. Specifically, the glass fiber fabric of the present embodiment can be produced by: the glass fiber of the present embodiment described above is woven by a weaving machine known per se as at least a part of the warp or weft. Examples of the loom include: jet looms such as air jet looms and water jet looms, shuttle looms, rapier looms, and the like. Further, as a weaving method of the weaving machine, for example, a plain weave, a satin weave, a basket weave, a twill weave, and the like can be cited, and from the viewpoint of manufacturing efficiency, a plain weave is preferably adopted. In the glass fiber fabric of the present embodiment, the glass fibers of the present embodiment are preferably used as warp yarns and weft yarns.

In the glass fiber fabric of the present embodiment, the glass fiber of the present embodiment is preferably a mass of 0.9 to 69.0tex (g/1000 m) obtained by bundling 35 to 400 glass filaments having a filament diameter of 3.0 to 9.0 μm and applying 0 to 1.0 twist/25 mm.

In the glass fiber fabric of the present embodiment, when the glass fiber of the present embodiment is used as warp or weft, it is preferable that the warp weaving density is 40 to 120 threads/25 mm and the weft weaving density is 40 to 120 threads/25 mm.

The glass fiber fabric of the present embodiment may be subjected to deoiling treatment, surface treatment, and splitting treatment after weaving.

Examples of the deoiling treatment include the following treatments: the glass fiber fabric is placed in a heating furnace with the atmosphere temperature of 350-400 ℃ for 40-80 hours, and the organic matter attached to the glass fiber is heated and decomposed.

Examples of the surface treatment include the following: the glass fiber fabric is impregnated in a solution containing the silane coupling agent or a solution containing the silane coupling agent and the surfactant, and after removing excess water, the glass fiber fabric is dried by heating at a temperature ranging from 80 to 180 ℃ for 1 to 30 minutes.

Examples of the fiber opening treatment include the following: the warp yarns of the glass fiber fabric are subjected to a tension of 30 to 200N, and at the same time, the yarn width of the warp yarns and the weft yarns is widened by opening with water pressure, opening with high-frequency vibration using liquid as a medium, opening with fluid pressure having surface pressure, opening with pressure of a roller, and the like.

The glass fiber fabric of the present embodiment preferably has a thickness of 7.0 to 190.0g/m ² The thickness is in the range of 8.0 to 200.0. Mu.m.

The glass fiber fabric of the present embodiment preferably has a warp yarn width of 110 to 600 μm and a weft yarn width of 110 to 600 μm.

The glass fiber fabric of the present embodiment may further include a surfactant containing the silane coupling agent or a surface treatment layer containing the silane coupling agent and the surfactant. When the glass fiber fabric of the present embodiment includes the surface-treated layer, the surface-treated layer has a mass in the range of, for example, 0.03 to 1.50 mass% with respect to the total amount of the glass fiber fabric including the surface-treated layer.

The glass fiber-reinforced resin composition of the present embodiment includes the glass fiber of the present embodiment described above. Specifically, in the glass fiber reinforced resin composition containing a resin (thermoplastic resin or thermosetting resin), glass fibers, and other additives, the glass fiber reinforced resin composition of the present embodiment contains 10 to 90 mass% of glass fibers with respect to the total amount of the glass fiber reinforced resin composition. The glass fiber reinforced resin composition of the present embodiment contains 90 to 10 mass% of resin relative to the total amount of the glass fiber reinforced resin composition, and contains other additives in the range of 0 to 40 mass%.

Here, examples of the thermoplastic resin include: <xnotran> , , , / , / , , / (AS) , // (ABS) , // (ACS) , // (AES) , / / (ASA) , / (SAN) , , (PVC), (PVDC), , , (PET), (PBT), (PTT), , , (PES), (PPSU), (PPE), (m-PPE), , (LCP), , (PEI), (PAR), (PSF), (PAI), (PABM), (TPI), (PEN), / (EVA) , (IO) , , / , </xnotran> Polybutene, polymethylpentene, olefin/vinyl alcohol resins, cyclic olefin resins, cellulose resins, polylactic acid, and the like.

Specifically, examples of the polyethylene include: high Density Polyethylene (HDPE), medium density polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), ultrahigh molecular weight polyethylene, and the like.

Examples of the polypropylene include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, and a mixture of the foregoing polypropylenes.

Examples of the polystyrene include general-purpose polystyrene (GPPS) which is atactic polystyrene having an atactic structure, high Impact Polystyrene (HIPS) in which a rubber component is added to GPPS, and atactic polystyrene having an atactic structure.

Examples of the methacrylic resin include: a polymer obtained by polymerizing one methacrylic resin selected from acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and fatty acid vinyl ester alone, or a polymer obtained by copolymerizing two or more of the methacrylic resins.

Examples of the polyvinyl chloride include: vinyl chloride homopolymers polymerized by a method known in the art, such as emulsion polymerization, suspension polymerization, microsuspension polymerization, or bulk polymerization, copolymers with monomers copolymerizable with vinyl chloride monomers, or graft copolymers obtained by graft-polymerizing vinyl chloride monomers onto polymers.

Examples of polyamides include: polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polyhexamethylene adipamide (nylon 106), polypentamethylene sebacamide (nylon 1010), polypentamethylene dodecanoamide (nylon 1012), polypentaundecanoamide (nylon 11), polyhexamethylene adipamide (nylon 116), polydodecanoamide (nylon 12), polyxylylene adipamide (nylon D6), polyxylylene sebacamide (nylon MXD 10), polymetaxylxylylene adipamide (nylon MXD 6), polyparaxylylene adipamide (nylon D6), polyparaxylylene adipamide (nylon 4T), polypentamethyleneterephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (nylon 9T 11T), polyhexamethylene terephthalamide (nylon 11T 12), polyhexamethylene terephthalamide (nylon 11T), poly (nylon 11T 12), poly (nylon 4T), poly (nylon 11T) and poly (nylon 11T) terephthalamide, one or a combination of two or more of poly (3-methyl-4-aminohexyl) methane terephthalamide (nylon PACMT), poly (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), poly (3-methyl-4-aminohexyl) methane dodecanamide (nylon PACM 12), poly (3-methyl-4-aminohexyl) methane tetradecanoamide (nylon PACM 14), and the like, or a mixture of the above component and the above copolymer.

Examples of the polyacetal include: homopolymers having an oxymethylene unit as a main repeating unit, and copolymers mainly composed of an oxymethylene unit and having an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain.

Examples of the polyethylene terephthalate include polymers obtained by polycondensation of ethylene glycol and terephthalic acid or a derivative thereof.

Examples of polybutylene terephthalate include polymers obtained by polycondensation of 1,4-butanediol and terephthalic acid or a derivative thereof.

Examples of the polytrimethylene terephthalate include polymers obtained by polycondensation of 1,3-propanediol and terephthalic acid or a derivative thereof.

Examples of the polycarbonate include: a polymer obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

Examples of the polyarylene sulfide include linear polyphenylene sulfide, crosslinked polyphenylene sulfide having a high molecular weight obtained by a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, polyphenylene sulfide ketone, and the like.

The polyphenylene ether includes: poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether), poly (2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene ether), poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4' -methylphenyl) -3272 zxft 72-phenylene ether ], poly (2-bromo-6-phenyl-3424 zxft 4984-phenylene ether), poly (2-methyl-6-phenyl-1,4-3584), poly (2-phenyl-3284-3584), poly (2-bromo-6-phenyl-3424 zxft) 3584), poly (2-methyl-6-phenyl-3535-chloro-4284), poly (2-chloro-4225-4223-chloro-3584), 6-di-n-propyl-1,4-phenylene ether), poly (2-methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether), and the like.

Examples of the modified polyphenylene ether include: a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) ether and a styrene/butadiene copolymer, a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) ether and a styrene/maleic anhydride copolymer, a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) ether and polyamide, a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) ether and a styrene/butadiene/acrylonitrile copolymer, a modified polyphenylene ether having functional groups such as amino groups, epoxy groups, carboxyl groups, styrene groups, etc. introduced into the polymer chain ends of the polyphenylene ether, a modified polyphenylene ether having functional groups such as amino groups, epoxy groups, carboxyl groups, styrene groups, methacryloyl groups, etc. introduced into the side chains of the polyphenylene ether polymer chain.

Examples of the polyaryletherketone include: polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone (PEKK), polyether ether ketone (PEEKK), and the like.

Examples of the Liquid Crystal Polymer (LCP) include (co) polymers composed of one or more structural units selected from the following components: examples of the thermotropic liquid crystalline polyester include an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, and an aliphatic dicarbonyl unit.

Examples of the fluororesin include: polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene resin (ECTFE), and the like.

Examples of the Ionomer (IO) resin include: and polymers obtained by neutralizing a part of the carboxyl group with a metal ion, such as copolymers of an olefin or styrene and an unsaturated carboxylic acid.

Examples of the olefin/vinyl alcohol resin include: ethylene/vinyl alcohol copolymers, propylene/vinyl alcohol copolymers, ethylene/vinyl acetate copolymer saponified materials, propylene/vinyl acetate copolymer saponified materials, and the like.

Examples of the cyclic olefin resin include: monocyclic bodies such as cyclohexene, polycyclic bodies such as tetracyclic cycloalkene, and polymers of cyclic olefin monomers.

Examples of polylactic acid include: poly-L-lactic acid as a homopolymer of the L form, poly-D-lactic acid as a homopolymer of the D form, or stereocomplex polylactic acid as a mixture thereof.

Examples of the cellulose resin include: methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, and the like.

In addition, examples of the thermosetting resin include: unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenol resin (PF), polyurethane resins (PU), polyisocyanates, polyisocyanurates, polyimides (PI), urea (UF) resins, silicon (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismaleimide Triazine (BT) resins, diallyl phthalate resins (PDAP) and the like.

Specifically, examples of the unsaturated polyester resin include resins obtained by esterification reaction of an aliphatic unsaturated dicarboxylic acid and an aliphatic diol.

Examples of the vinyl ester resin include: a bisvinyl ester resin and a novolak-type vinyl ester resin.

Examples of the epoxy resin include: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, bisphenol M-type epoxy resin (4,4 ' - (1,3-phenylenediisopropylidene) bisphenol-type epoxy resin), bisphenol P-type epoxy resin (4,4 ' - (1,4-phenylenediisopropylidene) bisphenol-type epoxy resin), bisphenol Z-type epoxy resin (4,4 ' -cyclohexene bisphenol-type epoxy resin), phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, tetraphenolethane novolac-type epoxy resin, novolac-type epoxy aromatic hydrocarbon having a condensed ring structure, biphenyl-type epoxy resin, xylylene-type epoxy resin, phenylaralkyl-type epoxy resin, or other aralkyl-type epoxy resin, naphthylene ether-type epoxy resin, naphthol-type epoxy resin, naphthalene diol-type epoxy resin, 2-functional or 4-functional naphthalene-type epoxy resin, binaphthyl-type epoxy resin, naphthalene aralkyl-type epoxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, fluorene-type epoxy resin, anthracene-type epoxy resin, fluorene-type epoxy resin, and the like.

Examples of the melamine resin include a polymer obtained by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

Examples of the phenolic resin include: a phenol novolac type phenol resin such as phenol novolac resin, cresol novolac resin, bisphenol a type phenol novolac resin, a methylol type resol resin, a methylol ether type resol resin, or a resol type resol resin such as a dimethylene ether type resol resin, or a resin such as an arylalkylene type resol resin, or a resin obtained by combining two or more kinds of resins.

The urea resin includes a resin obtained by condensation of urea and formaldehyde.

The thermoplastic resin or the thermosetting resin may be used alone, or two or more kinds of resins may be used in combination.

The glass fiber reinforced resin composition of the present embodiment is used in applications where low dielectric characteristics are required, and therefore, an epoxy resin, a modified polyphenylene ether, polybutylene terephthalate, polypropylene, a fluororesin, or a Liquid Crystal Polymer (LCP) is preferable as the resin.

Examples of the other additives include: reinforcing fibers other than glass fibers (e.g., carbon fibers and metal fibers), fillers other than glass fibers (e.g., glass powder, talc, and mica), flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flowability improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, and pigments.

The glass fiber reinforced resin composition of the present embodiment may be a prepreg obtained by impregnating the glass fiber fabric of the present embodiment with the resin by a method known per se and semi-curing the resin.

The glass fiber reinforced resin composition of the present embodiment can be molded into various glass fiber reinforced resin molded articles by known molding methods such as injection molding, injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid foam molding), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, press molding, fusion molding, hand lay-up molding, spray molding, resin transfer molding, sheet molding, bulk molding, pultrusion molding, and filament winding. Further, by curing the prepreg, a glass fiber reinforced resin molded article can be obtained.

Examples of the applications of the glass fiber reinforced resin molded article include: electronic device cases, electronic components (printed wiring boards), vehicle exterior parts (bumpers, fenders, hoods, airbags, wheel covers, etc.), vehicle interior parts (door trims, roof materials, etc.), vehicle engine peripheral parts (oil pans, hoods, intake manifolds, exhaust manifolds, etc.), muffler-related parts (muffler parts, etc.), high-pressure tanks, and the like.

The glass fiber of the present embodiment can be used for the glass fiber-reinforced resin composition of the present embodiment, and can also be applied to a reinforcing material for an inorganic material such as gypsum and cement. For example, when used as a reinforcing material for gypsum (particularly, gypsum board having a thickness of 4 to 60 mm), the gypsum contains glass fibers having the above composition range in an amount of 0.1 to 4.0% by mass based on the total mass of the gypsum.

Next, examples of the present invention and comparative examples are shown.

Examples

First, glass raw materials were mixed to obtain a glass batch material such that the glass compositions after melt-solidification became the compositions of examples 1 to 5 and comparative examples 1 to 5 shown in table 1.

Next, a glass batch corresponding to the glass composition for glass fibers of examples 1 to 5 or comparative examples 1 to 5 was melted at 1550 ℃ for 6 hours to obtain a homogeneous glass cullet (glass pellet). Next, the glass cullet was placed in a platinum crucible having a diameter of 80mm, and a melt melted at 1500 ℃ for 4 hours was taken out of the crucible to obtain a glass gob. Subsequently, the obtained glass block was annealed at 580 ℃ for 8 hours to obtain a test piece. Then, the dielectric loss tangent and the phase separation property of the test piece obtained above were measured or evaluated by the following methods. In addition, the 1000 poise temperature was measured using the glass chips obtained in the test piece production process.

Further, glass batch materials corresponding to the glass compositions for glass fibers of examples 1 to 5 or comparative examples 1 to 5 or the glass cullet described above were melted at 1550 ℃ in a glass melting furnace to obtain a melt, and the melt was discharged from a bushing having a nozzle plate in which 200 nozzle heads were formed, cooled, and solidified to obtain glass beads (glass beads). The obtained glass beads were subjected to slow cooling from 580 ℃ for 8 hours, and then the striae characteristics of the glass beads were evaluated by the method shown below using at least 40 slowly cooled glass beads.

The evaluation results are shown in table 1.

[ method of measuring dielectric loss tangent ]

The test piece was polished to obtain a polished test piece of 80 mm. Times.3 mm (thickness: 1 mm). Subsequently, the obtained polishing test piece was dried absolutely and stored in a room at a temperature of 23 ℃ and a humidity of 60% for 24 hours. Next, the dielectric loss tangent (dissipation ratio Df) at 10GHz of the polishing test piece obtained above was measured in accordance with JIS C2565.

[ evaluation method of phase separation Properties ]

The disc-shaped test piece was allowed to stand on the boundary between the black plate and the white plate, and the boundary surface between the black plate and the white plate was observed through the test piece from the upper surface of the test piece. If white turbidity (phase separation) is not observed in the test piece and the boundary surface can be clearly observed, it is evaluated as "a", if the boundary surface can be clearly observed although fine white turbidity is observed in the test piece, it is evaluated as "B", and if the boundary surface cannot be clearly observed due to white turbidity in the test piece, it is evaluated as "C".

[ method of measuring 1000 poise temperature ]

The 1000 poise temperature was determined by: the glass cullet was melted in a platinum crucible using a high temperature electric furnace with a rotary viscometer (manufactured by zhipu systems corporation), the viscosity of the molten glass was continuously measured using a rotary Brookfield (ブルックフィールド) type viscometer while changing the melting temperature, and the temperature corresponding to the rotary viscosity of 1000 poise was measured.

[ evaluation method of Rib characteristics ]

The glass beads were observed by an optical microscope at a magnification of 20 to 50 times, and the number of observed glass beads having striae was measured. When the ratio of the number of glass beads observed with striae to the total number of glass beads was 40% or less, the total number of glass beads was evaluated as "a"; when the ratio exceeded 40% and was 60% or less, it was evaluated as "B"; when the ratio exceeds 60%, it is evaluated as "C".

[ Table 1]

As shown in table 1, the glass compositions for glass fibers of the present invention shown in examples 1 to 5 contain, relative to the total amount of the glass compositions for glass fibers: siO in the range of 52.0 to 57.5 mass%, B in the range of 19.5 to 25.5 mass% ₂ O ₃ And 8.0 to 13.0 mass% of Al ₂ O ₃ MgO in a range of 0 to 2.0 mass%, caO in a range of 0 to 6.0 mass%, srO in a range of 0.5 to 6.5 mass%, tiO in a range of 0.1 to 3.0 mass% ₂ ，Al ₂ O ₃ Content ratio (mass%) of (B) to the B ₂ O ₃ The content (mass%) of (B) (Al) ₂ O ₃ /B ₂ O ₃ ) In the range of 0.35 to 0.54, the SiO ₂ Content ratio (mass%) of (B) SI ₂ O ₃ A content (mass%) B of the above-mentioned MgO, a content (mass%) M of the above-mentioned CaO, a content (mass%) C of the above-mentioned SrO, a content (mass%) SR of the above-mentioned SrO, and the above-mentioned TiO ₂ The glass composition for glass fiber of the present invention having the above composition has a low dielectric loss tangent (dielectric loss tangent of 0.0018 or less), suppresses the occurrence of phase separation, reduces the viscosity at high temperatures (1000 poise temperature of 1375 ℃ or less), and reduces the occurrence of striae, while satisfying the following formula (1).

6.90≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤12.30…(1)

On the other hand, in the case of using the glass compositions for glass fibers in comparative examples 1 to 5, since the composition does not satisfy the above formula (1), there are caused any one or more of the disadvantages that the dielectric loss tangent is high (the dielectric loss tangent exceeds 0.0018), phase separation is caused, the viscosity at high temperature is not lowered (the 1000 poise temperature exceeds 1375 ℃), or striae are caused.

[ example 6]

Glass raw materials were mixed so that the composition of the glass after melting and solidification would be the same as that of example 1, to obtain a glass batch. Next, the glass batch was melted at 1550 ℃, and the obtained melt was discharged from a bushing having a nozzle plate with 200 nozzle tips formed thereon, and wound at a predetermined speed, and cooled and solidified while being drawn, thereby forming glass fibers (glass filaments) having a perfectly circular cross section and a fiber diameter of 5 μm. The 200 glass filaments obtained above were bundled by applying a bundling agent to the filaments by an applicator, and wound up in a collet (Colette) to obtain a glass fiber bundle. The series of operations (spinning) was continued for 6 hours, so that no breakage of the glass fibers occurred.

Comparative example 6

Glass raw materials were mixed so that the composition of the glass after melt-solidification became the same composition as in comparative example 5, to obtain a glass batch. Next, the glass batch was melted at 1550 ℃, and the obtained melt was discharged from a bushing having a nozzle plate with 200 nozzle tips formed thereon, and wound at a predetermined speed, and cooled and solidified while being drawn, thereby forming glass fibers (glass filaments) having a perfectly circular cross section and a fiber diameter of 5 μm. The 200 glass filaments obtained above were bundled by applying a bundling agent to the filaments by an applicator, and wound up in a collet to obtain a glass fiber bundle. The series of operations (spinning) was continued for 6 hours, as a result of which 15 breaks of the glass fibers occurred.

From the results of example 6 and comparative example 6, it was confirmed that if the glass composition for glass fiber of the present invention is used, the production can be performed while suppressing the breakage of the glass fiber and the glass fiber bundle. In addition, if the number of times of breakage of the glass fiber is 7 or less in the case of continuous spinning for 6 hours, it falls within an allowable range in industrial production. Thus, the glass composition for glass fiber of the present invention sufficiently satisfies the above-mentioned criteria. In the case of industrially producing glass fibers, the number of breaks when the glass fibers are continuously spun for 6 hours is preferably 5 or less, more preferably 3 or less, and still more preferably 1 or less.

Claims

1. A glass composition for glass fibers, characterized in that,

containing, relative to the total amount of glass composition used for the glass fiber: siO in the range of 52.0 to 57.5 mass% ₂ 19.5 to 25.5% by mass of B ₂ O ₃ 8.0 to 13.0 mass% of Al ₂ O ₃ MgO in a range of 0 to 2.0 mass%, caO in a range of 0 to 6.0 mass%, srO in a range of 0.5 to 6.5 mass%, and TiO in a range of 0.1 to 3.0 mass% ₂ ，

The Al is ₂ O ₃ Content of (B) based on the amount of B ₂ O ₃ The content ratio (mass%) of (B) is Al ₂ O ₃ /B ₂ O ₃ In the range of 0.35 to 0.54,

the SiO ₂ Content ratio (mass%) of (B) SI ₂ O ₃ A content (mass%) B of the above-mentioned MgO, a content (mass%) M of the above-mentioned CaO, a content (mass%) C of the above-mentioned SrO, a content (mass%) SR of the above-mentioned SrO, and the above-mentioned TiO ₂ The content (mass%) T satisfies the following formula (1):

6.90≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤12.30…(1)。

2. the glass composition for glass fiber according to claim 1, wherein the SI, B, M, C, SR, and T satisfy the following formula (2):

9.56≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.77…(2)。

3. the glass composition for glass fibers according to claim 2, wherein the SI, B, M, C, SR, and T satisfy the following formula (3):

10.00≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤11.35…(3)。

4. the glass composition for glass fiber according to claim 3, wherein the SI, B, M, C, SR, and T satisfy the following formula (4):

10.15≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.85…(4)。

5. the glass composition for glass fiber according to claim 4, wherein the SI, B, M, C, SR, and T satisfy the following formula (5):

10.35≤100×(B/SI) ² ×{SR/(C+SR)} ^2/3 ×{T/(M+T)} ^1/2 ≤10.78…(5)。

6. a glass fiber formed from the glass composition for glass fiber of any one of claims 1 to 5.

7. A glass fiber fabric comprising the glass fiber according to claim 6.

8. A glass fiber-reinforced resin composition comprising the glass fiber according to claim 6.